Preparation of perfluorodimethyl peroxide



United States Patent M 3,1tl0,803 PREPARATIQN 0F EERFLUGRSDWETHYL Roger 5. Porter, @rinda, Calit., and George H. Cady, Seattle, Wash, assignors, by mesne assignments, to the United States of America as represented by the Secretary of the Navy No Drawing. Filed Sept. 8, 1959, Ser. No. 833,389

1 Claim. (Cl. 265-610) This invention relates to the preparation and production of perfluorodimethyl peroxide a compound of the empirical formula, C F O The structural formula prob ably is The object of the invention is to provide a good method for producing the compound.

It has heretofore been known that perfluorodimethyl peroxide is produced in small yield by the electrolysis of an aqueous solution containing trifluoroacetate ion ['F. Swarts, Bull. soc. chim. Belg. 42, 102 (1933)] but only very small amounts have been obtained. The method is costly because of the low eficiency in utilization of materials. The present invention uses materials efficiently and is capable of producing large amounts of perfluorodimethyl peroxide at a much lower cost than was formerly possible.

Perfluorodimethyl peroxide is an oxidizing agent capable of supporting the combustion of hydrocarbons and other fuels. It is of potential value as an oxidant for fuels in rocket propulsion. Since it is a peroxide, it may be expected to be of value for causing polymerization reactions to occur.

The inventors now disclose that perfluorodimethyl peroxide is formed by combining carbonyl fluoride with trifluoromethyl hypofluorite. The reaction may be represented by the equation:

They also disclose that the peroxide may be prepared by combining fluorine with carbon monoxide or with carbonyl fluoride. Fluorinating catalysts such as the higher fluorides of metals belonging to the class including AgF CuF CoF CeF HgF SbF Feb}, and NiF induce the reaction. In the case of carbonyl fluoride, it is probable that fluorine reacts to give trifluoromethyl hypofluorite as shown in Equation 2 COF2+F2 cr on 2 and that the hypofluorite combines with unchanged carbonyl fluoride as shown in Equation 1.' When carbon monoxide is used as the starting material, it first reacts with fluorine to give carbonyl fluoride as shown in Equa- CO+F2- COF2 (3) The carbonyl fluoride may then give perfluorodimethyl peroxide by Reactions 2 and 1. These equations and the theoretical discussion are given at this point to make tion 3:

7 clear the nature of the invention and to show that the 3,ljfl0,803 Patented Aug. 13, 1963 fluoride and :trifluoromethyl hypofluorite. When both of these products are present in a reacting mixture, one may expect to obtain perfluorodimethyl peroxide. Perfluorodimethyl peroxide can be produced by reacting carbon monoxide, carbon dioxide or carbonyl fluoride with either fluorine or' trifluorornethyl hypofluorite.

In order that a high yield of perfluorodimethyl peroxide may be obtained by the reaction of fluorine with carbonyl fluoride or carbon monoxide, or by the reaction of carbonyl fluoride with triflucromethyl hypofluorite, it is necessary that the temperature and the relative proportions of the reactants be held within certain limits. The yield also is dependent upon the length of time allowed for the reaction and upon the presence or absence of a catalyst.

Four different reaction vessels have been used by the inventors to prepare perfluorodimethyl peroxide. Vessel A was a cylindrical container made of nickel. 'It had a volume of 1.71 liters and it could be heated to any desired temperature by electrical heaters. Its temperature was measured by thermocouples. The reactants were added separately to this vessel and their pressures were measured. As the vessel was heated, the course of a reaction involving a pressure change was followed by measuring the total pressure of the mixture of gases. Samples of gas were sometimes removed from the vessel for identification and anaylsis.

The second reaction vessel (vessel B) was constructed of copper tubing. It was used to study reactions under conditions of continuous flow. The two gaseous reactants entered (by separate inlets) a cylindrical mixing chamber having an internal diameter of 4.1 cm. and a length of 9.0 cm. They passed through this chamber and then through an electrically heated tube of 89 cm. length and 1.7 cm. internal diameter. When carbon monoxide and fluorine were used as the reactants much heat was liberated in the mixing chamber. If rapid flows of these gases were to be used in a large scale plant, it would be desirable to cool the reactor near the inlets for reactants.

A third reaction vessel (vessel C) was also constructed from copper tubing. It was packed with a tangled mass of copper ribbon of 0.035 cm. Width and 0.008 cm. thickness. This ribbon weighed 4500 g. and before use it was plated with 100 g. of silver. As the result of use, the silver metal became converted to fluorides of silver. The reaction vessel had a length of cm. and an internal diameter of 7.5 cm. It could be heated bypassing electricity through coils of resistance wire wound over a layer of asbestos paper surrounding the reactor. There were two heating coils. This made it possible to control the temperature separately in each end of the reactor. At one end of the reactor the two gaseous reactants entered, each by its own inlet, and at the other end the products departed through an outlet.

The fourth reaction vessel (vessel D) was a steel cylinder of the type commonly used to store gases. its capacity was approximately five liters. Its inner surface was conditioned by long exposure to fluorine; :then the cylinder Was used in the laboratory as a storage tank for trifluoromethyl hypofluorite, CF OF.

When using each type of apparatus it was possible to collect samples of the products by condensing them in traps cooled by liquid oxygen. Such samples were analyzed by distillation, the substances being recognized by their boiling points and otherproperties.

Example 1.-Equimolar amounts ot trifluoromethyl hypofluorite and carbonyl fluoride were placed in vessel A at 27 C. giving :a total pressure of |1 6.l cm. of mercury. The vessel was heated slowly to 287 C. Up to 225 C. the pressure increased in proportion to the absolute temperatune, thereby indicating not more than a little cornbination of the two gases. Above about 235 C. the

' peroxide. This experiment showed that the rate of reaction of Ihifluoromethyl hypofluorite with carbonyl fluoride became appreciable at about 230 C. it also showed that'the rate increased with rising temperature above 230 C. (as indicated by an increase in the rate of pressure change). Since the reaction was slow in the neighborhood of 230 C. to 250 C., it follows that the duration of contact or the reactants in a continuous flow reactor at this temperature is important in determining the yieldoi perfluorodimethyl peroxide.

Vessel A was also used to study the decomposition of perfluorcdirnethyl peroxide. A sample of the gas was heated slowly to 420 C. All: about 225 C. the substance started to decompose, as shown by an abnormally great increase in pressure with temperature. At approximately 325 C. the decomposition was substantially complete. This experiment shows that it is desirable when preparing perfluorodimethylperoxide to keep the temperature of the reactants as low as possible while still obtaining the desired product. When a continuous ,tlo-w reactor is used at temperatures above 325 C., one may obtain perflucrodimethyl peroxide, but it is probable that much of the product is formed as the temperature of the gas halls, upon leaving the reactor.

Example .2.-$everal runs were made using reaction vessel B to determine the effect of temperature and of the relative concentrations of the reactants upon the yield of periluorodimcthyl peroxide. tered one inlet and fluorine the other. The total pressure within the system was substantially one atmosphere. The reaction conditions and the yields of perfluorodimethyl peroxide are given in liable 1. The yield of C F O shown in column 5 was calculated from the equation:

Preparation of Perfluorodimethyl Peroxide in Vessel B Rates of flow, liters per hour 1 Run Reactor at room temp. Yield Other products (111 N o. temp, and pressure 014F502, much, 1 little) percent CO Fr 2- 405 2. 20 3.05 21 H1COF9, Elk-CF30]? 8- 405 1. 00 3.05 Below 1 II1OF3OF, m-Fg 4- 400 0.90 1. 55 21 Ill-CF3OF, m-COF: 5- 307 2.17 3.10 17 m-CFaOF, mCOF 6- 307 2.17 3. 90 8 m-OFaOF, l-COFz 7 307 2.10 4. 30 Trace I11CF3OF 8 307 2.17 2. 50 7 4 II1-GOF2, lOF3OF 9- 307 2 20 3.30 21 m-GOF mCF3OF 10... 240 2 17 3. 25 10 IBFOOFZ, 1-OF3OF, l-

2 1l 200 2.20 3. 25 Below 1 mCOF mF l- CF2OF 12 25 0 0 Below 1 m-OOF m-F 1 In run 12 the reactor was filled at room temperature by passing F2 and CO at rates of 3.20 L/hr. aud'2.15 1./hr. respectively. The gases then stood for 28 hours, At the end of this time the gas contained COFe and F Neither (321 002 nor CFsOF' were observed to be present in amounts as great as 1% of the total product.

The tollowing conclusions were drawnfrom the experiments described in Table 1: (1) To obtain perfluorodimethyl peroxide rapidly the temperature of the reactor needed to be greater than 200 C. (2) The best yield of perfluorodimethyl peroxide was obtained with an F to CO ratio of 3 to 2. This corresponded to the equation:

zco+sr =cr oocr 4 Carbon monoxide en- 7 (3) When the ratio of F 'ito CO was greater than to 1,

I fromusing COF and F in a. volume-ratio of 2 to 1 as required by the not equation V 2COF +F =F COOCF (5) tained from continuous gas streams through vesselB was about 21% of that theoretically possible. The yield was independent of temperature from 307 C. up to the highest temperature used, 405 C. Since Example il indicated thatthe peroxide should not have been obtained above about 325 C., it is likely thattne perfluorodirnethyl 5 peroxide obtained with vessel B at its higher temperatures was formed as the gas became cooler while passing through the outlet tube leading from the reactor.

Runs 11 and 12 of Table 1 showed'th at carbonyl fluoride was formed from fluorine and carbon monoxide whenthe temperature of the reactor was'held below about 200 C. but that the formation of pcrfiuorodimcthyl peroxide must have been very slow. Unreacted fluorine remained mixed with the carbonyl fluoride. electrical heating of the reactor was used, it was possible to tell that the reaction to dorm carbonyl fluoride occurred in the mixing chamber. This became warm to the touch (perhaps C.) but the tube of 89 cm. length remained at about 25 C. Runs which produced perfiuonodirnetheyl peroxide must have done so by [the reaction of carbonyl fluoride with fluorine in the heated tube of vessel B. This series of experiments showed that perfluorodirnethyl peroxide was produced by the reaction of fluorine with carbon monoxide or with carbonyl fluoride. The best yields of perfluorodimethyl peroxide resulted Example 13.Vessel C was used, the region near the gas inlets being at 76 C. and the region near the outlet being at about 183 C. Fluorine was passed at a rate of 3.25 liters per hour lmdcarbon monoxide at 2.20 liters per hour (each measured at about 25 C. and one atmosphere pressure). The yield of perfluorodimethyl peroxide was about 58% of that theoretically possible from the lanrounfof carbon monoxide consumed. Both carbonyl fluoride and trifluor-omeinyl hypo-fluorite were obtained as by-products. In another run made in vessel C no electrical heating was used. The temperature near the inlet was about 5 0 C. and near the outlet was about 27 C. Rates of flow of gases measured liters per. hour at about 25 C. and one atmospherewere: F 2.90; CO, 2.15; N (diluent), 4.0. When a sample of the product was distilled, no perfluorodiincthyl peroxide was found. A small amount probably was present. If so, however, it distilled with the carbonyl fluoride. The gas contained fluorine and rnuch carbonyl fluoride. in the case of this run the gas streams were shut off [and the mixture was allowed to stand in the apparatus at about 25 C. for 23 hours. A sample of the gas was then removed. The product contmned CF OF, COF and perfluorodimethyl peroxide approximately in the volume ratio; 2 to 5 to :8 respectively.

The runs in Example 3 showed that the first step in the process was the production of carbonyl fluoride as shown in Equation 3 and that this was followed by addithat vessel C contained a catalyst for the formation of perfluorodimethyl peroxide and that the catalyst was the tangled mass of copper ribbon bearing a surface layer formed by the fluorination of silver. f

Example 4.A two to one ratio by volume of fluorine When no and carbon dioxide was heated in vessel A to about 325 C. and was then cooled slowly to room temperature. The resulting mixture of gas contained about ten percent per- -fluorodirnethyl peroxide.

Example 5.Trifluoromethy1 hypofluorite was stored at room temperature in vessel D for a period somewhat over one year. At first the gas contained some carbonyl fluoride as an'impurity but little or no perfluorodimethyl peroxide was present. At the end of the storage period a part of the gas was condensed and distilled. An appreciable amount of perfluorodirnethyl peroxide then was present. This example shows that trifluonomethyl hypofluorite and carbonyl fluoride react even at room temperature to form perfluorodirnethyl peroxide. From Examples 1 and 2 it is evident that the reaction at room temperature (about 25 C.) is very slow.

Summary.( 1) Perfluorodimethyl peroxide may be obtained in the following ways: (a) combining carbonyl fluoride with trifluoromethyl hypofluorite, (b) combining carbon monoxide with fluorine, (c) combining carbonyl fluoride with fluorine, (d) reacting carbon dioxide with fluorine. Any combination of reactants which forms both carbonyl fluoride and trifluoromethyl hypofluorite should also be capable of forming perfluorodimethyl peroxide.

(2) The preferred proportions of reactants are in each case those required by the stoichiometry of the reactions. A range of concentrations may be used in each case. For carbon monoxide and fluorine it is best that the ratio by volume lie within the limits 1 to 1 up to 1 of CO to 2 of F For fluorine and carbonyl fluoride it is desirable that the ratio of F to COF be less than 1.

200 C. The reaction occurs at temperatures as low as 25 C. but it is slow. Even though perfluorodimethyl per-oxide decomposes at temperatures below 3-25 C., it is possible to produce the substance with the reactor (at least in part) at higher temperatures than this. Apparently the upper temperature limit is that at which the rate of corrosion of the reactor by fluorine becomes large. For a nickel vessel this temperature is about 500 C.

(4) Copper, coated with silver fluoride(s) serves as a catalyst for the preparation of perfluorodimethyl peroxide. When it is present, reaction temperatures as low as 25 C. rnay'be used. This application is a continuation in part of our prior copending application Serial Number 655,948, filed April 30, 1957, and now abandoned.

What we claim is:

A process for producing perfluorodimethyl peroxide which comprises contacting carbonyl fluoride and trifluoromethyl hypofluorite within the temperature range 225 C. to 325 C.

OTHER REFERENCES Kellogg et al.: 1 our. Amer. Chem. Soc., vol (1948), pages 3986- (five pages).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 100 803 August 13, 1963 Roger S. Porter et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below Column 3, line 4, for "1.1 cm." read 11.1 cm.

column 4, line 25. for "8O C. read '70 C.

Signed and sealed this 14th day of April 1964.

(SEAL) Attest:

EDWARD J. BRENNER ERNEST W. SWIDER Attesting Officer Commissioner of Patents 

